CN112011187B - Addition-curable silicone resin composition, method for producing same, and optical semiconductor device - Google Patents
Addition-curable silicone resin composition, method for producing same, and optical semiconductor device Download PDFInfo
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Abstract
The invention provides an addition-curable silicone resin composition which gives a silicone cured product having a low refractive index, high transparency even when used under high-temperature conditions, and little change in hardness and reduction in mass. The addition-curable silicone resin composition comprises, in specific blend amounts: an organopolysiloxane having an alkenyl group and a fluoroalkyl group; (B) an organosilicon compound having a hydrogen atom; (C) a platinum group metal-based catalyst; and (D) i) an organopolysiloxane having a fluoroalkyl group, ii) a carboxylate containing a cerium rare earth element, and iii) (R) 4 O) 4 Ti (in the formula, R 4 Monovalent hydrocarbon groups of the same kind or different kinds) or a partial hydrolysis condensate thereof.
Description
Technical Field
The present invention relates to an addition-curable silicone resin composition, a method for producing the composition, and an optical semiconductor device.
Background
As a die bonding material for a light emitting diode (hereinafter, referred to as "LED") element, it has been proposed to use a silicone resin (patent documents 1 to 3). Silicone resins have been proposed to be mainly used for blue LEDs and white LEDs because they are superior in heat resistance, weather resistance, and discoloration resistance as compared with conventional epoxy resins.
However, the solid-crystal materials composed of these conventional silicone resin materials are mainly composed of methyl silicone resin compositions, and cannot sufficiently satisfy the optical device performance, and particularly, the transmittance for light of 400nm is not necessarily high.
On the other hand, patent document 4 proposes an addition-curable silicone composition that gives an elastomer having a low refractive index, good transparency, and excellent light extraction efficiency, by a silicone composition containing a perfluoroalkyl group bonded to a silicon atom, and a sealing material for an optical element formed from the composition. However, the weight of the fluorosilicone resin having a perfluoroalkyl group is greatly reduced at high temperatures, and an increase in hardness associated therewith occurs. In the LED, a decrease in weight and an increase in hardness cause serious errors such as cracks, and it is desired to solve these problems.
Patent document 5 reports a heat-resistant silicone rubber composition containing a mixture of rare earth salts of 2-ethylhexanoic acid, and further reports that a sheet having a thickness of 2mm has a transmittance of 90% or more for light having a wavelength of 600 nm. However, the heat-resistant silicone rubber composition has a problem of poor light transmittance for short-wavelength light having a wavelength of around 400 nm. Further, such a heat resistance improver is not compatible with a fluorine silicone resin having a perfluoroalkyl group, and is separated with time, and thus, heat resistance of a cured product cannot be expressed or transparency is impaired.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 11-1619
Patent document 2: japanese patent laid-open publication No. 2002-265787
Patent document 3: japanese patent laid-open publication No. 2004-186168
Patent document 4: japanese patent laid-open publication No. 2013-010881
Patent document 5: japanese patent No. 5422755
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide an addition-curable silicone resin composition that gives a silicone cured product having a low refractive index, high transparency even when used under high-temperature conditions, and little change in hardness and reduction in quality.
Means for solving the problems
In order to achieve the above object, the present invention provides an addition-curable silicone resin composition comprising:
(A) One molecule has more than 2 alkenyl groups bonded to silicon atoms and more than 1 CF bonded to silicon atoms 3 -(CF 2 ) a -(CH 2 ) b -a group represented by(wherein a is an integer of 3 or more, and b is an integer of 1 or more);
(B) An organosilicon compound having 2 or more silicon atom-bonded hydrogen atoms in one molecule, in an amount such that the silicon atom-bonded hydrogen atoms in the component (B) are 0.5 to 5.0 atoms per 1 silicon atom-bonded alkenyl group in the component (a);
(C) A platinum group metal catalyst in an amount of 1 to 500ppm in terms of the mass of the platinum group metal relative to the total mass of the component (A) and the component (B); and
(D) A reaction product of the following components i), ii) and iii), which is 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the components (A) and (B):
i) A viscosity at 25 ℃ of 10 to 10,000mPas, and at least 1 CF bonded to a silicon atom in one molecule 3 -(CF 2 ) j -(CH 2 ) k An organopolysiloxane of the group represented by (wherein j is an integer of 3 or more and k is an integer of 1 or more),
ii) a carboxylate containing a rare earth element of cerium in an amount of 0.05 to 5 parts by mass of cerium with respect to 100 parts by mass of the component i),
iii)(R 4 O) 4 ti (in the formula, R 4 Is a monovalent hydrocarbon group of the same kind or different kind) or a partial hydrolysis condensate thereof in an amount such that titanium is 0.05 to 5 parts by mass relative to 100 parts by mass of the component i).
The addition-curable silicone resin composition provides a silicone cured product that has a low refractive index, exhibits excellent transmittance for light having a wavelength of around 400nm even when used under high temperature conditions, and has little hardness change and little mass loss.
Preferably, the component (B) has 1 or more CF bonded to a silicon atom in one molecule 3 -(CF 2 ) f -(CH 2 ) g A group represented by (wherein f is an integer of 0 or more, and g is an integer of 1 or more).
When the component (B) has the fluoroalkyl group, the addition-curable silicone resin composition gives a cured product having a low refractive index, and when used under high-temperature conditions, the cured product has more excellent transmittance for light having a wavelength of around 400nm, and has less change in hardness and less decrease in mass.
Preferably: in the component (a), a =5 and b =2, and in the component (D), j =5 and k =2.
When the component (a) is an organopolysiloxane having a specific fluoroalkyl group and the component (D) is produced using an organopolysiloxane having a specific fluoroalkyl group, the addition-curable silicone resin composition gives a silicone cured product having a low refractive index, and when used under high-temperature conditions, has more excellent transmittance for light having a wavelength of around 400nm, and has less hardness change and less mass loss.
The addition-curable silicone resin composition preferably has a refractive index at 25 ℃ of 1.37 or less for light having a wavelength of 589 nm.
When the addition-curable silicone resin composition exhibits a refractive index of the prescribed value or less, the addition-curable silicone resin composition gives a silicone cured product having a further excellent light extraction efficiency.
The present invention also provides a method for producing the addition-curable silicone resin composition, comprising a step of reacting the components i), ii), and iii) at a temperature of 150 ℃ or higher while bubbling an oxygen-containing gas, thereby producing the component (D).
By the method for producing an addition-curable silicone resin composition, it is possible to produce an addition-curable silicone resin composition that gives a cured product having a low refractive index, excellent transmittance for light having a wavelength of around 400nm even when used under high-temperature conditions, and little change in hardness and reduction in mass.
Further, the present invention provides a cured silicone product which is a cured product of the addition-curable silicone resin composition.
The silicone cured product has a low refractive index, has excellent transmittance for light having a wavelength of about 400nm even when used under high temperature conditions, and has little hardness change and mass reduction.
Preferably, the silicone cured product has a transmittance of 80% or more for light having a wavelength of 400nm when the optical length is 2 mm.
Even when used under high temperature conditions, the silicone cured product exhibiting the light transmittance of at least the above-mentioned predetermined value has further excellent transmittance for light having a wavelength of around 400 nm.
The present invention also provides an optical semiconductor device in which an optical semiconductor element is die-bonded using the silicone cured product, and an optical semiconductor device in which an optical semiconductor element is sealed using the silicone cured product.
These optical semiconductor devices have high reliability.
Effects of the invention
The addition-curable silicone resin composition of the present invention gives a cured product that has a low refractive index, exhibits excellent transmittance for light having a wavelength of around 400nm even when used under high-temperature conditions, and is less susceptible to hardness change and mass loss. Therefore, the addition-curable silicone resin composition of the present invention is particularly useful as a material for protecting and sealing an LED element, a material for changing and adjusting a wavelength, a material for forming a die bond or a lens, or a material for other optical devices or optical parts.
Detailed Description
As described above, there has been a demand for the development of an addition-curable silicone composition having a low refractive index, excellent transmittance to light having a wavelength of around 400nm when used under high-temperature conditions, and reduced hardness change and mass loss.
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by an addition-curable silicone resin composition containing the following components (a) to (D), and that the composition is suitable as an LED material or the like, and have completed the present invention.
That is, the present invention is an addition-curable silicone resin composition containing:
(A) One molecule has more than 2 alkenyl groups bonded to silicon atoms and 1CF having more than one bonded to silicon atom 3 -(CF 2 ) a -(CH 2 ) b An organopolysiloxane of the group represented (wherein, a is an integer of 3 or more, b is an integer of 1 or more);
(B) An organosilicon compound having 2 or more silicon atom-bonded hydrogen atoms in one molecule, in an amount such that the silicon atom-bonded hydrogen atoms in the component (B) are 0.5 to 5.0 atoms per 1 silicon atom-bonded alkenyl group in the component (a);
(C) A platinum group metal catalyst in an amount of 1 to 500ppm in terms of the mass of the platinum group metal relative to the total mass of the component (A) and the component (B); and
(D) A reaction product of the following components i), ii) and iii), which is 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B):
i) A viscosity at 25 ℃ of 10 to 10,000mPas, and at least 1 CF bonded to a silicon atom in one molecule 3 -(CF 2 ) j -(CH 2 ) k An organopolysiloxane of the group represented by (wherein j is an integer of 3 or more and k is an integer of 1 or more),
ii) a carboxylic acid salt containing a rare earth element of cerium in an amount of 0.05 to 5 parts by mass of cerium with respect to 100 parts by mass of the component i),
iii)(R 4 O) 4 ti (in the formula, R 4 Is a monovalent hydrocarbon group of the same kind or different kind) or a partial hydrolysis condensate thereof in an amount such that titanium is 0.05 to 5 parts by mass relative to 100 parts by mass of the component i).
The present invention will be described in detail below, but the present invention is not limited thereto.
[ addition-curable Silicone composition ]
The addition-curable silicone resin composition of the present invention contains the following components (a) to (D):
(A) One molecule has more than 2 alkenyl groups bonded to silicon atoms and more than 1 CF bonded to silicon atoms 3 -(CF 2 ) a -(CH 2 ) b An organopolysiloxane of the group represented (wherein a is an integer of 3 or more, and b is an integer of 1 or more);
(B) An organosilicon compound having 2 or more hydrogen atoms bonded to silicon atoms in one molecule;
(C) A platinum group metal-based catalyst;
(D) The reaction product of the following i), ii) and iii):
i) A viscosity at 25 ℃ of 10 to 10,000mPas, CF having at least 1 bond to a silicon atom in one molecule 3 -(CF 2 ) j -(CH 2 ) k An organopolysiloxane of the group represented by (wherein j is an integer of 3 or more and k is an integer of 1 or more),
ii) a carboxylic acid salt containing a rare earth element of cerium,
iii)(R 4 O) 4 ti (in the formula, R 4 Monovalent hydrocarbon groups of the same kind or different kinds) or a partial hydrolysis condensate thereof.
Hereinafter, each component will be described in detail.
< component (A) >
(A) The component (A) is a compound having in one molecule 2 or more alkenyl groups bonded to silicon atoms and 1 or more CF groups bonded to silicon atoms 3 -(CF 2 ) a -(CH 2 ) b An organopolysiloxane of the group (wherein a is an integer of 3 or more and b is an integer of 1 or more) which contributes to a reduction in refractive index of the addition-curable silicone resin composition and the silicone cured product.
(A) The component (B) may be linear or branched, and may be liquid, wax-like or solid.
Examples of the alkenyl group bonded to a silicon atom in the component (a) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like, and an alkenyl group having 2 to 10 carbon atoms is preferable, an alkenyl group having 2 to 6 carbon atoms is particularly preferable, and a vinyl group is more preferable.
a is an integer of 3 or more, preferably an integer of 3 to 9, and more preferably 5. If a is less than 3, a sufficient reduction in refractive index may not be achieved.
b is an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2. In terms of manufacturing level, b is not preferably 0.
As such CF 3 -(CF 2 ) a -(CH 2 ) b -a group represented by, preferably CF 3 -(CF 2 ) 3 -(CH 2 ) 2 -a group represented by, CF 3 -(CF 2 ) 5 -(CH 2 ) 2 -a group represented.
The component (A) may have CF bonded to a silicon atom in addition to the fluoroalkyl group 3 -(CF 2 ) d -(CH 2 ) e A group represented by (wherein d is an integer of 0 to 2 and e is an integer of 1 to 5), and from the viewpoint of raw material procurement and synthesis, CF is preferred 3 -(CH 2 ) 2 -a group represented.
The substituent other than the alkenyl group and the fluoroalkyl group bonded to the silicon atom in the component (a) is not particularly limited, and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is preferable. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl and cyclopentyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; and chloroalkyl groups such as chloromethyl, chloropropyl, and chlorocyclohexyl. Preferably an alkyl group, more preferably a methyl group.
Examples of the component (a) include linear organopolysiloxanes represented by the following formula (1).
[ chemical formula 1]
In the formula, R 1 Are optionally identical or different alkenyl radicals, R 2 Is an optionally same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms other than the alkenyl group, R f1 Are optionally identical or different fluoroalkyl radicals, R f1 Is CF 3 -(CF 2 ) a -(CH 2 ) b A group represented by (wherein a is an integer of 3 or more and b is an integer of 1 or more). w is an integer of 1-3, x, y and z are integers of x being more than or equal to 0, y being more than or equal to 1 and z being more than or equal to 0 respectively. The siloxane units in parentheses with x, y, z can be in any order.
x is an integer of 0 or more, preferably 0 to 10, and y is an integer of 1 or more, preferably 2 to 20, and more preferably 5 to 10. z is an integer of 0 or more, preferably an integer of 0 to 10, and more preferably an integer of 0 to 5. x + y + z is preferably 1 to 30, more preferably 2 to 20, and further preferably 5 to 12. The value of y/(x + y + z) is preferably in the range of 1/20 to 1/1, more preferably 1/10 to 1/1, and still more preferably 1/5 to 1/1.
The component (A) may have SiO 4/2 Unit (Q unit) or R 2 SiO 3/2 A branched organopolysiloxane (R) comprising at least one siloxane unit represented by unit (T unit) 2 And the above-mentioned R 2 The same).
The branched organopolysiloxane may further contain (R) units such as methylvinylsiloxy units, dimethylsiloxy units and the like 2 ) 2 SiO 2/2 Units (D units), dimethylvinylsiloxanyl units, trimethylsiloxy units, and the like (R) 2 ) 3 SiO 1/2 Unit (M unit) (R) 2 And the above-mentioned R 2 The same), the total content of the Q unit and the T unit is preferably 5 mol% or more, more preferably 10 to 95 mol%, further preferably 20 to 80 mol%, and particularly preferably 20 to 60 mol% of all siloxane units in the component (a).
The weight average molecular weight of the component (A) is preferably in the range of 500 to 100,000 in view of ease of handling.
Specific examples of the component (a) include organopolysiloxanes represented by the following structural unit ratios.
[(CH 3 ) 3 SiO 1/2 ] 0.10 [(CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ] 0.17 [SiO 4/2 ] 0.29 [CF 3 -(CF 2 ) 5 -CH 2 -CH 2 -SiO 3/2 ] 0.44
[(CH 2 ＝CH)(CH 3 )SiO 2/2 ] 0.16 [(CF 3 -CH 2 -CH 2 )SiO 3/2 ] 0.78 [(CF 3 -(CF 2 ) 3 -CH 2 -CH 2 )(CH 3 )SiO 2/2 ] 0.05
[(CH 2 ＝CH)(CH 3 )SiO 2/2 ] 0.12 [CF 3 -(CF 2 ) 5 -CH 2 -CH 2 -SiO 3/2 ] 0.35 [CH 3 SiO 3/2 ] 0. 53
In the above formula, the order of arrangement of the siloxane units is arbitrary.
< ingredient (B) >
(B) The component (c) is an organosilicon compound having 2 or more hydrogen atoms (i.e., siH groups) bonded to silicon atoms in one molecule. (B) Component (a) functions as a crosslinking agent that crosslinks with the alkenyl groups contained in component (a) by a hydrosilylation reaction.
The component (B) is not particularly limited as long as it is an organosilicon compound having 2 or more hydrogen atoms bonded to silicon atoms in one molecule, and examples thereof include organohydrogensilanes and organohydrogenpolysiloxanes, and organohydrogenpolysiloxanes are preferable. The molecular structure of the organohydrogenpolysiloxane is not particularly limited, and examples thereof include linear, cyclic, branched, and three-dimensional network structures (resin structures).
(B) The number of SiH groups in the component (B) is preferably 2 to 200, more preferably 3 to 100 per 1 molecule. When the organosilicon compound of the component (B) has a linear or branched structure, these SiH groups may be located at either one of the molecular chain ends or non-molecular chain end portions, or may be located at both of the molecular chain ends and non-molecular chain end portions.
(B) The number of silicon atoms (degree of polymerization) in one molecule of the organosilicon compound of component (a) is preferably 2 to 1,000, more preferably 3 to 200, and still more preferably 4 to 100.
Further, it is preferable that the organosilicon compound of the component (B) is a liquid at 25 ℃ and that the kinematic viscosity at 25 ℃ measured with a Cannon-Finsk viscometer is 1 to 1,000mm 2 S, more preferably 10 to 300mm 2 /s。
In the component (B), the substituent bonded to the silicon atom other than the SiH group is not particularly limited, but preferably does not have an aliphatic unsaturated group, and examples thereof include an unsubstituted monovalent hydrocarbon group, and a monovalent hydrocarbon group substituted with a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), an epoxy group-containing group (e.g., an epoxy group, a glycidyl group, and a glycidyl ether oxy group), an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, and a butoxy group), and the like. Examples of such a substituted or unsubstituted monovalent hydrocarbon group include preferably an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a group obtained by substituting these groups with the above-mentioned substituents. Further, when the monovalent hydrocarbon group has an epoxy group-containing group and/or an alkoxy group as a substituent, adhesiveness can be imparted to a cured product of the addition-curable silicone resin composition of the present invention.
From the viewpoint of further lowering the refractive index, it is preferable that the silicon-bonded substituent in the component (B) has CF 3 -(CF 2 ) f -(CH 2 ) g A group represented by (wherein f is an integer of 0 or more, and g is an integer of 1 or more).
As CF 3 -(CF 2 ) f -(CH 2 ) g -a group represented by, preferably CF 3 -(CH 2 ) 2 -、CF 3 -(CF 2 ) 3 -(CH 2 ) 2 -、CF 3 -(CF 2 ) 5 -(CH 2 ) 2 -a group represented.
Specific examples of the component (B) include organohydrogenpolysiloxanes represented by the following formula (2).
R 3 h H i SiO (4-h-i)/2 (2)
In the formula, R 3 Is a substituted or unsubstituted monovalent hydrocarbon group optionally identical or different, which does not contain an alkenyl group, h and i are numbers satisfying 0.7. Ltoreq. H.ltoreq.2.1, 0.001. Ltoreq. I.ltoreq.1.0, and 0.8. Ltoreq. H + i.ltoreq.3.0, preferably numbers satisfying 1.0. Ltoreq. H.ltoreq.2.0, 0.01. Ltoreq. I.ltoreq.1.0, and 1.5. Ltoreq. H + i.ltoreq.2.5.
As R 3 The substituted or unsubstituted monovalent hydrocarbon group of (2) is not particularly limited as long as it has no alkenyl group, and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is preferred. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl and cyclopentyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; chloromethyl, chloropropyl, chlorocyclohexyl, CF 3 -(CF 2 ) e -(CH 2 ) f - (wherein e is an integer of 0 or more and f is an integer of 1 or more), and the like.
Wherein, as R 3 Preferably alkyl and haloalkyl, more preferably methyl and CF 3 -(CH 2 ) 2 -、CF 3 -(CF 2 ) 3 -(CH 2 ) 2 -、CF 3 -(CF 2 ) 5 -(CH 2 ) 2 -a group represented.
The organohydrogensiloxane represented by the average compositional formula (2) may contain a monoorganosiloxane unit (M unit), a diorganosiloxane unit (D unit), a triorganosiloxane unit (T unit), and/or SiO that do not contain SiH groups 4/2 The units (Q units), but preferably 30 to 70 mol% of all organosiloxane units are methylhydrogensiloxane units.
<xnotran> (B) , 5363 zxft 5363- , 3242 zxft 3242- , ( ) , ( ) , , - , , - , - , - , - - , - - , , , - , - , - , , , </xnotran> And a dimethylhydrogensiloxyalkyl group-blocked diphenylsiloxane-methylhydrogensiloxane copolymer at both ends of the molecular chain, and an organohydrogenpolysiloxane in which some or all of the methyl groups in each of the above exemplified compounds are substituted with other alkyl groups such as ethyl groups and propyl groups.
As a preferred specific example of the component (B), a structural unit ratio [ CF ] can be mentioned 3 -(CF 2 ) 5 -(CH 2 ) 2 SiO 3/2 ] 0.25 [H(CH 3 ) 2 SiO 1/2 ] 0.75 Polysiloxane (in the above formula, the order of arrangement of siloxane units is arbitrary).
(B) One component may be used alone, or two or more components may be used simultaneously.
(B) The amount of component (a) blended is such that the number of silicon atom-bonded hydrogen atoms (SiH groups) in component (B) is 0.5 to 5.0 per 1 silicon atom-bonded alkenyl group in component (a), that is, the amount of component (B) blended is such that the number of silicon atom-bonded hydrogen atoms (SiH groups) in component (B) is 0.5 to 5.0 times the total number of all silicon atom-bonded alkenyl groups in component (a). From the viewpoint of the balance of crosslinking, the number of silicon atom-bonded hydrogen atoms (SiH groups) in the component (B) is preferably 0.7 to 3.0 times the total number of all silicon atom-bonded alkenyl groups in the component (a). If the amount is less than 0.5 times, crosslinking tends to be insufficient, and if the amount exceeds 5.0 times, crosslinking tends to progress insufficiently or excessively, and a silicone cured product having excellent hardness cannot be obtained.
Component (C)
(C) The platinum group metal-based catalyst of the component (a) is a component for promoting and accelerating the hydrosilylation reaction between the component (a) and the component (B).
The platinum group metal catalyst is not particularly limited, and examples thereof include platinum group metals such as platinum, palladium, and rhodium; platinum compounds such as chloroplatinic acid, alcohol-modified chloroplatinic acid, and coordination compounds of chloroplatinic acid with olefins, vinylsiloxanes, and acetylene compounds; a platinum group metal compound such as tetrakis (triphenylphosphine) palladium or tris (triphenylphosphine) rhodium chloride, etc., and a catalyst obtained by organosilicon-modifying chloroplatinic acid has good compatibility with the component (a) and the component (B), and contains almost no chlorine impurity, which is preferable.
(C) One component may be used alone, or two or more components may be used simultaneously.
The amount of the component (C) to be incorporated is 1 to 500ppm, preferably 3 to 100ppm, and more preferably 5 to 40ppm in terms of the mass of the platinum group metal element relative to the total mass of the components (A) and (B). If the blending amount of the component (C) is less than 1ppm, the resulting addition-curable silicone resin composition will not be sufficiently cured, and on the other hand, even if the blending amount exceeds 500ppm, the curing speed of the addition-curable silicone resin composition will not be increased even higher, and it is not economical.
< ingredient (D) >
(D) The component (a) is a reaction product of the following components i), ii) and iii), exhibits high compatibility with the components (a) to (C), and is an additive for imparting heat resistance to an addition-curable silicone resin composition.
i) A viscosity at 25 ℃ of 10 to 10,000mPas, and at least 1 CF bonded to a silicon atom in one molecule 3 -(CF 2 ) j -(CH 2 ) k An organopolysiloxane of the group represented by (wherein j is an integer of 3 or more, and k is an integer of 1 or more);
ii) a carboxylate containing a rare earth element of cerium in an amount of 0.05 to 5 parts by mass of cerium with respect to 100 parts by mass of the component i);
iii)(R 4 O) 4 ti (in the formula, R 4 Is a monovalent hydrocarbon group of the same kind or different kind) or a partial hydrolysis condensate thereof in an amount such that titanium is 0.05 to 5 parts by mass relative to 100 parts by mass of the component i).
(i) The organopolysiloxane of component (A) has a viscosity at 25 ℃ of 10 to 10,000mPas, preferably 100 to 7000 mPas. If the viscosity is less than 10 mPas, the volatile matter will be volatilized during the reaction, and if the viscosity is higher than 10,000mPas, the handling becomes difficult.
CF in component (i) 3 -(CF 2 ) j -(CH 2 ) k In the group represented by (a), j is an integer of 3 or more, preferably an integer of 3 to 9, and more preferably 5. If j is less than 3, the compatibility with the component (A) is poor, and the transparency of the addition-curable silicone resin composition and the silicone cured product is impaired.
k is an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2. In terms of manufacturing level, k is not preferably 0.
As such CF 3 -(CF 2 ) j -(CH 2 ) k -a group represented by, preferably CF 3 -(CF 2 ) 3 -(CH 2 ) 2 -a group represented by, CF 3 -(CF 2 ) 5 -(CH 2 ) 2 -a group represented.
Specific examples of the component i) include a structural unit ratio [ (CH) 3 ) 3 SiO 1/2 ] 0.2 [(CH 3 )SiO 3/2 ] 0.4 [CF 3 -(CF 2 ) 5 -(CH 2 ) 2 SiO 3/2 ] 0.4 The polysiloxane represented by the formula (I), and the like.
Examples of the carboxylate of the rare earth element as the component ii) include salts of cerium with 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid, stearic acid, and the like.
In the component iii), as R 4 The monovalent hydrocarbon group of (2) is exemplified by the group represented by the formula (1) above as R 2 The same groups as those shown in the examples are preferably alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl and the like.
Examples of the titanium compound as the component iii) include titanium tetraalkoxide such as tetra-n-butyl titanate, and a hydrolysis-condensation product thereof.
(D) The component (b) is a reaction product obtained by reacting the components i), ii) and iii) at a temperature of 150 ℃ or higher while bubbling an oxygen-containing gas.
The oxygen-containing gas preferably contains 5 vol% or more of oxygen gas with respect to the whole gas supplied by bubbling, and a mixed gas of an inert gas such as nitrogen or argon and oxygen gas, air, or the like can be used.
The amount of component (D) to be blended is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total of components (A) and (B). If the blending amount of the component (D) exceeds the above range, the obtained addition-curable silicone resin composition may be colored or the hardness of the silicone cured product may be reduced. If the amount of component (C) is less than the above range, sufficient thermal discoloration resistance cannot be obtained.
< other ingredients >
In addition to the components (a) to (D), other components exemplified below may be blended in the addition-curable silicone resin composition of the present invention.
(reaction inhibitor)
If necessary, a conventionally known reaction inhibitor (reaction regulator) which is a compound having a curing inhibitory effect on the addition reaction catalyst of the component (C) can be used in the addition-curable silicone resin composition of the present invention. Examples of the reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; a sulfur-containing compound; acetylene compounds; a hydroperoxide compound; maleic acid derivatives, and the like.
Since the degree of the curing inhibition effect by the reaction inhibitor varies significantly depending on the chemical structure of the reaction inhibitor, it is preferable to adjust the blending amount of the reaction inhibitor to an optimum amount for each reaction inhibitor used. In general, it is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the component (A), the component (B), the component (C) and the component (D).
(adhesion improver)
The addition-curable silicone resin composition of the present invention may contain an adhesion improver for improving the adhesion thereof. Examples of the adhesion improving agent include a silane coupling agent and a hydrolysis-condensation product thereof. Examples of the silane coupling agent include known silane coupling agents such as an epoxy group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, an isocyanate group-containing silane coupling agent, an isocyanurate group-containing silane coupling agent, an amino group-containing silane coupling agent, and a mercapto group-containing silane coupling agent, and 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass can be used with respect to 100 parts by mass of the total of the components (a) and (B). The adhesion improver may have the above-mentioned adhesive functional group and may contain an alkenyl group or a hydrogen atom bonded to a silicon atom. At this time, the component (A) and the component (B) undergo a hydrosilylation reaction and enter the reaction system.
(Filler)
The addition-curable silicone resin composition of the present invention can be filled with an inorganic filler such as crystalline silica, a hollow filler, or silsesquioxane, or a filler obtained by hydrophobizing the surface of the filler with an organic silicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organoazane compound, or a low-molecular-weight siloxane compound; silicone rubber powder, silicone resin powder, and the like. As the component, a filler capable of imparting thixotropy is particularly preferably used, and by imparting thixotropy, a silicone cured product excellent in handling properties and mechanical properties can be obtained.
The addition curable silicone resin composition of the present invention can be prepared in the following manner: the above-mentioned components (a) to (D) and other components used as needed are mixed by a known method using a planetary mixer (planetary mixer) or the like to prepare the composition.
The addition-curable silicone resin composition of the present invention may be a two-part composition prepared by separately preparing a first reagent and a second reagent, and mixing the first reagent and the second reagent before use, wherein the first reagent comprises the component (a), the component (C), the component (D), and, if necessary, other components; the second reagent is composed of the component (A), the component (B), the component (D) and, if necessary, other components. Further, the reagent may have a component commonly used in the first reagent and the second reagent. By forming the addition-curable silicone resin composition into such a two-part form, the storage stability can be further ensured.
The addition-curable silicone resin composition of the present invention preferably has a refractive index (nD 25) at 25 ℃ for light having a wavelength of 589nm of 1.40 or less.
When the addition-curable silicone resin composition exhibits a refractive index of the prescribed value or less, the addition-curable silicone resin composition gives a silicone cured product having a further excellent light extraction efficiency.
[ cured product ]
Further, the present invention provides a cured product of the addition-curable silicone resin composition (silicone cured product).
The cured silicone is highly transparent even when used under high temperature conditions, has reduced hardness variation and mass reduction, and is particularly useful as a sealing material for LED elements and the like. In particular, since the addition-curable silicone composition of the present invention has a fluoroalkyl group or the like in the component (a), the component (D), and optionally the component (B), a silicone cured product having a low refractive index, improved light transmittance, and excellent light extraction efficiency can be obtained.
The silicone cured product of the present invention preferably has a transmittance of 80% or more for light having a wavelength of 400nm when the optical length is 2 mm.
The addition-curable silicone resin composition of the present invention may be cured under known conditions, and for example, it may be cured at 100 to 180 ℃ for 10 minutes to 5 hours.
The addition-curable silicone resin composition of the present invention can be used as a coating material and a sealing material for semiconductor elements, particularly semiconductor elements for optical applications such as LED elements, a die bonding material, and a protective coating material for electrical and electronic applications.
[ optical semiconductor device ]
Further, the present invention provides an optical semiconductor device in which an optical semiconductor element is die-bonded or sealed using the silicone cured product.
The addition-curable silicone resin composition of the invention can give a silicone cured product with high transparency and little change in hardness and mass loss even when used under high-temperature conditions. Therefore, the optical semiconductor device using the silicone cured product has high reliability.
As an example of a method for die bonding an optical semiconductor element using the addition-curable silicone resin composition of the present invention, the following method can be mentioned: the addition-curable silicone resin composition of the present invention is filled in a syringe, applied to a substrate such as a package (package) using a dispenser (dispenser) so that the thickness is 5 to 100 μm in a dry state, and then an optical semiconductor element (for example, a light-emitting diode) is disposed on the applied addition-curable silicone resin composition, and the composition is cured, whereby the optical semiconductor element is die-bonded on the substrate. Further, the following method may be used: the addition curing type silicone resin composition is placed on a doctor blade (squeegee dish), and after the addition curing type silicone resin composition is coated on a substrate by a method of dispensing (holding) while the doctor blade (squeegee) is applied so that the thickness is 5 to 100 μm in a dry state, an optical semiconductor element is disposed on the coated addition curing type silicone resin composition, and the composition is cured, whereby the optical semiconductor element is subjected to crystal fixing on the substrate. The curing conditions of the addition-curable silicone resin composition may be set as described above. Thus, an optical semiconductor device having high reliability and having an optical semiconductor element bonded with a crystal using the cured silicone of the present invention can be obtained.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, the viscosity is a value at 25 ℃ measured using a rotary viscometer, and the kinematic viscosity is a value at 25 ℃ measured using a cannon-fenske viscometer. Further, the abbreviations for the respective siloxane units have the following meanings.
M：(CH 3 ) 3 SiO 1/2
M H ：H(CH 3 ) 2 SiO 1/2
D Vi ：(CH＝CH 2 )(CH 3 )SiO 2/2
D F3 ：CF 3 -(CH 2 ) 2 (CH 3 )SiO 2/2
D F13 ：CF 3 -(CF 2 ) 5 -(CH 2 ) 2 (CH 3 )SiO 2/2
T：(CH 3 )SiO 3/2
T F13 ：CF 3 -(CF 2 ) 5 -(CH 2 ) 2 SiO 3/2
[ Synthesis example 1]
2340.0g of (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) trimethoxysilane, 202.5g of hexamethyldisiloxane, 680g of methyltrimethoxysilane and 52g of methanol were charged into a 3L four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, and 6.6g of methanesulfonic acid and further 80.3g of water were added dropwise while stirring. 500g of hexafluorom-xylene was added and the reaction was carried out at 65 ℃ for 5 hours, followed by dropwise addition of 10.7g of a 50% aqueous solution of potassium hydroxide. Methanol was distilled off by heating, and the reaction was carried out at 120 ℃ for 5 hours. Further 3.4g of methanesulfonic acid was added, neutralization reaction was carried out at 110 ℃ for 2 hours, and then 6.9g of KYOWAAD was added500 (Kyowa Chemical Industry Co., ltd.) and stirred at 25 ℃. The obtained solution was filtered, and then concentrated under reduced pressure at 120 ℃ to remove the solvent, whereby an organopolysiloxane having a viscosity of 5,300mPas and a refractive index of 1.35 was obtained. The organopolysiloxane obtained has a structural unit ratio M based on NMR spectroscopy 0.2 T 0.4 T F13 0 .4。
[ Synthesis example 2]
To 130 parts by mass of the organopolysiloxane obtained in synthesis example 1, 13 parts by mass (0.55 parts by mass in terms of cerium) of a turpentine (turpentine) solution of 2-ethylhexanoate containing a cerium rare earth element mixture (the rare earth element content is 6% by mass) and 2.7 parts by mass (the mass of titanium is 0.85 times the mass of cerium in the 2-ethylhexanoate) of a mixture of tetra-n-butyl titanate were added under stirring to obtain a yellowish white dispersion. Air was bubbled into the dispersion at a pressure of 0.1MPa (flow rate: 0.3L/min), and while nitrogen gas was circulated through the reaction vessel, heating was carried out to remove turpentine. Then, the mixture was heated at 300 ℃ for 1 hour to obtain a reddish brown and transparent composition (D-1).
[ comparative Synthesis example 1]
To 130 parts by mass of an average formula M 2 D F3 To the organopolysiloxane (refractive index: 1.38, viscosity: 450mPa · s) shown above, a turpentine solution (rare earth element content: 6 mass%) of 2-ethylhexanoate containing a cerium rare earth element mixture, 13 parts by mass (0.55 parts by mass in terms of cerium), and a solution of 2.7 parts by mass (titanium mass: 0.85 times the mass of cerium in the 2-ethylhexanoate) of tetrabutyl titanate were previously mixed with sufficient stirring to obtain a yellowish white dispersion. Air was bubbled into the dispersion at a pressure of 0.1MPa (flow rate: 0.3L/min), and while nitrogen gas was circulated in the reaction vessel, heating was performed to remove turpentine. Then, the mixture was heated at 300 ℃ for 1 hour to obtain a reddish brown and transparent composition (D-2).
[ Synthesis example 3]
The platinum catalyst (C-1) was prepared by diluting the reaction product of hexachloroplatinic (IV) acid (platinum hexamine) and 1,3-divinyltetramethyldisiloxane with an ethanol solution so that the platinum content was 3 mass%.
Examples 1 and 2 and comparative examples 1 and 2
The following components were mixed in the blending amounts (parts by mass) shown in table 1 to prepare an addition curable silicone composition.
(A) The components:
(A-1) structural Unit ratio T F13 0.35 T 0.53 D Vi 0.12 Organopolysiloxane (refractive index 1.36, viscosity 49Pa · s)
(B) The components:
(B-1) structural Unit ratio T F13 0.25 M H 0.75 The organohydrogenpolysiloxane (kinematic viscosity 2.5 mm) represented 2 /s)、
(B-2) structural Unit ratio D F13 0.17 D F3 0.5 M H 0.33 The organohydrogenpolysiloxane (kinematic viscosity 230 mm) shown 2 /s)
(C) The components:
(C-1) platinum catalyst obtained in Synthesis example 3
(D) The components:
(D-1) composition obtained in Synthesis example 2,
(D-2) comparison of the compositions obtained in Synthesis example 1
Other components:
(E-1) Compound represented by the following structural formula
[ chemical formula 2]
[ Table 1]
[ SiH ]/[ alkenyl ]: the number of SiH groups in component (B) to 1 alkenyl group bonded to silicon atom in component (A)
The following evaluations were performed on the addition-curable silicone resin compositions obtained in examples 1 and 2 and comparative examples 1 and 2, and the results are shown in table 2.
[ appearance ]
The appearance of each composition was observed with the naked eye.
[ refractive index ]
The refractive index (nD 25) of light having a wavelength of 589nm at 25 ℃ was measured using a refractometer (ATAGO CO., manufactured by LTD., RX-5000).
[ light transmittance ]
An addition-curable silicone resin composition was injected into a mold so as to have a thickness of 2mm, and cured by heating at 150 ℃ for 2 hours to obtain a silicone cured product, and the light transmittance of direct light having a wavelength of 400nm at 25 ℃ was measured using a spectrophotometer U-3900 (manufactured by High-Tech Science corporation) for the silicone cured product immediately after the silicone cured product was prepared and after the silicone cured product was stored at 250 ℃ for 250 hours.
[ hardness ]
The addition-curable silicone resin composition was heated and cured at 150 ℃ for 2 hours to obtain a silicone cured product, and the type a (TypeA) hardness of the silicone cured product at 25 ℃ was measured for the silicone cured product immediately after the silicone cured product was prepared and after the silicone cured product was stored at 250 ℃ for 250 hours. The rate of change in hardness was determined from the following equation.
(Change Rate%) = ((hardness after 250 ℃ C., 250 hours) ÷ (hardness immediately after production) × 100) -100
[ Mass remaining percentage after Heat resistance test ]
The mass of the cured silicone material used for the measurement of the light transmittance after 250 hours of storage in an environment at 250 ℃ was measured assuming that the initial mass was 100.
[ Table 2]
As shown in table 2, it is understood that the cured products obtained from the addition-curable silicone compositions of examples 1 and 2 are excellent in transparency and have little change in physical properties in the heat resistance test.
On the other hand, since comparative example 1 does not contain the component (D), the hardness change and the mass change in the heat resistance test are large, and the heat resistance is poor. Further, CF having fluoroalkyl group 3 -CH 2 -CH 2 The composition (D-2) of comparative example 2 in which an organopolysiloxane of the-group was used as the reaction component had poor compatibility with the components (A) to (C), poor transparency of the addition-curable silicone composition, poor transparency of the cured silicone product, and slightly large changes in hardness and mass.
In addition, the present invention is not limited to the above embodiments. The above embodiments are merely illustrative, and any embodiment having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operation and effect is included in the scope of the present invention.
Claims (11)
1. An addition-curable silicone resin composition characterized by comprising:
(A) One molecule has more than 2 alkenyl groups bonded to silicon atoms and more than 1 CF bonded to silicon atoms 3 -(CF 2 ) a -(CH 2 ) b An organopolysiloxane of the group represented by (a), wherein a is an integer of 3~9 and b is an integer of 1 or more;
(B) An organosilicon compound having 2 or more silicon atom-bonded hydrogen atoms in one molecule, in an amount such that the silicon atom-bonded hydrogen atoms in the component (B) are 0.5 to 5.0 atoms relative to 1 silicon atom-bonded alkenyl group in the component (a);
(C) A platinum group metal catalyst in an amount of 1 to 500ppm in terms of mass of platinum group metal relative to the total mass of the component (A) and the component (B); and
(D) A reaction product of the following components i), ii) and iii), which is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total of the components (A) and (B):
i) Viscosity at 25 ℃ is from 10 to 10, 000mPas, one minuteCF having at least 1 atom of its nucleus bonded to a silicon atom 3 -(CF 2 ) j -(CH 2 ) k An organopolysiloxane of the group represented by (a) wherein j is an integer of 3~9, k is an integer of 1 or more,
ii) a carboxylate containing a rare earth element of cerium in an amount of 0.05 to 5 parts by mass per 100 parts by mass of the component i),
iii)(R 4 O) 4 at least one of a compound represented by Ti and a partial hydrolysis-condensation product thereof in an amount of 0.05 to 5 parts by mass of titanium per 100 parts by mass of the component i), wherein R is 4 Are monovalent hydrocarbon groups of the same kind or different kinds,
the component (B) has 1 or more CF bonded to a silicon atom in one molecule 3 -(CF 2 ) f -(CH 2 ) g -wherein f is an integer of 0~5 and g is an integer of 1 or more.
2. The addition-curable silicone resin composition according to claim 1, wherein in component (a), a =5 and b =2, and in component (D), j =5 and k =2.
3. The addition-curable silicone resin composition according to claim 1, wherein the refractive index at 25 ℃ for light having a wavelength of 589nm is 1.37 or less.
4. The addition-curable silicone resin composition according to claim 2, wherein the refractive index at 25 ℃ for light having a wavelength of 589nm is 1.37 or less.
5. A process for producing the addition curable silicone resin composition of claim 1~4 comprising the step of reacting the components i), ii) and iii) at a temperature of 150 ℃ or higher while bubbling an oxygen-containing gas therethrough to produce the component (D).
6. A cured silicone product which is a cured product of the addition curable silicone resin composition according to any one of claims 1~4.
7. The cured silicone product according to claim 6, wherein the transmittance of light having a wavelength of 400nm is 80% or more at an optical path length of 2 mm.
8. An optical semiconductor device, characterized in that an optical semiconductor element is die-bonded using the silicone cured product according to claim 6.
9. An optical semiconductor device, which is characterized in that an optical semiconductor element is subjected to die bonding using the silicone cured product according to claim 7.
10. An optical semiconductor device, wherein an optical semiconductor element is sealed using the cured silicone according to claim 6.
11. An optical semiconductor device, wherein an optical semiconductor element is sealed using the cured silicone according to claim 7.
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